Process of producting ether compound

ABSTRACT

A method of production of an ether compound from an acetal compound or a ketal compound which is excellent in conversion and selectivity and does not cause corrosion of apparatuses and a novel useful polyvinyl ether compound as lubricating oil for compression-type refrigerators, electric insulation oil and the like are disclosed. The method of production of the present invention comprises reaction of an acetal compound or a ketal compound with hydrogen in the presence of a solid catalyst having acidic property and hydrogenation ability to produce the corresponding ether compound.

This application is a Divisional application of application Ser. No.066,238, filed May 25, 1993, now U.S. Pat. No. 5,399,631.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is related to a novel method of producing an ethercompound and to a novel polyvinyl ether compound. More particularly, thepresent invention is related to a method of efficiently producing auseful ether compound having a wide range of applications as solvent,lubricating oil and the like by hydrogenation of an acetal compound or aketal compound and a novel polyvinyl ether compound useful aslubricating oil for compression-type refrigerators, electric insulationoil, organic solvent, surface active agent and the like.

2. Description of the Related Arts

As the method of producing an ether compound from acetal compounds orketal compounds, for example, a method of using a combination of an acidand an alkali metal hydride, a method of using a silicon reagent and amethod of using diborane or the like are shown in "Jikken Kagaku Koza",Volume 20, the 4th edition (published by Maruzen). However, thesereactions use stoichiometric amounts of very expensive materials likethe alkali metal hydride, diborane and the silicon reagent as thehydrogenating reagent and are not preferable as the method of industrialproduction.

A method of a combination of an acid catalyst and catalytichydrogenation is known. W. L. Howard [J. Org. Chem. Volume 26, Page 1026(1961)] reported formation of an ether by catalytic hydrocracking of aketal by using a catalyst in which rhodium is supported on alumina inthe presence of hydrochloric acid. In the specification of the U.S. Pat.No. 4,088,700, a method of production of an ether compound by catalytichydrocracking of 1,3-dioxoranes which are cyclic acetals by using aplatinum catalyst or a rhodium catalyst in the presence of a Lewis acidsuch as boron trifluoride, aluminum trichloride and the like is shown.However, because these methods of production use hydrochloric acid,boron trifluoride, aluminum trichloride and the like, corrosion of theapparatus becomes the problem when the ordinary apparatus is used and aspecial treatment is necessary, making the method unfavorable.

As the method without using acids, for example, methods of producing anether compound by hydrocracking of acetals by a palladium catalystsupported on carbon were proposed in Japanese Patent Application LaidOpen No. 1983-4739 and Japanese Patent Application Laid Open No.1983-177929. Though these methods do not have the problem of corrosionof apparatus because they do not use acids, conversion of the materialacetal is not satisfactory. In these methods, a processes for separatingthe product and the materials from each other and recycling thematerials is necessary and this is not preferable. Furthermore, when theether formed cannot be separated and purified by distillation or thelike, the acetal is left in the product. Because acetals in general arelacking in stability, particularly in resistance to hydrolysis,aldehydes formed from them have oxidation, reduction, polycondensationand the like reactions to cause problem of deterioration of propertiesof the product to a great extent. Thus, the range of application ofthese methods is inevitably very limited.

Thus, a method of production of the ether compound from an acetalcompound or a ketal compound which has sufficient reaction activity,shows good selectivity and does not cause corrosion of the apparatus hasnot been discovered yet and development of such a method is stronglydesired.

Compression-type refrigerators are generally constituted with acompressor, a condenser, an expansion valve and an evaporator and has astructure that mixed fluid of refrigerant and lubricating oil iscirculated in this closed system. In the compression-type refrigerator,generally temperature is 50° C. or higher in the compressor and about-40° C. or lower in the refrigerating chamber although the temperatureis defferent depending on kind of apparatus and it is generally requiredthat the refrigerant and the lubricating oil are circulated in thesystem without causing phase separation in the range of temperature of-40° C. to +50° C. When the phase separation occurs during the operationof the refrigerator, life and efficiency of the apparatus are adverselyaffected to a great extent. For example, when the phase separation ofthe refrigerant and the lubricating oil occurs in the part of thecompressor, lubrication of the moving parts is deteriorated and seizureoccurs to cause decrease of life of the apparatus to a great extent.When the phase separation occurs in the evaporator, efficiency of heatexchange is decreased because of the presence of lubricating oil of highviscosity.

Because the lubricating oil for refrigerators is used for the purpose oflubricating moving parts in refrigerators, the lubricating property isnaturally important. Particularly, because the temperature in thecompressor is high, the viscosity which can hold the oil film necessaryfor the lubrication is important. The required viscosity is differentdepending on the kind of the compressor used and conditions of use andit is generally preferable that viscosity (kinematic viscosity) of thelubricating oil before mixing with the refrigerant is 5 to 1000 cSt at40° C. When the viscosity is lower than this range, oil film becomesthin to cause insufficient lubrication, and, when the viscosity ishigher than this range, the efficiency of the heat exchange isdecreased.

Electric refrigerators have the motor and the compressor built into asingle body and lubricating oil for them is required to have a highdegree of electric insulating property. In general, a volume specificresistance of 10¹² Ω·cm or more at 80° C. is required. When theresistance is lower than this value, possibility of leak of electricityarises.

As the refrigerant for compressor-type refrigerators, mainlydichlorodifluoromethane (referred to as Flon 12 hereinafter) hasheretofore been used and, as the lubricating oil, various kinds ofmineral oil and synthetic oil satisfying the required propertiesdescribed above have been used. However, chlorofluorocarbons (CFC)including Flon 12 are being more rigorously restricted world-widebecause they cause environmental pollution such as the rupture of theozone layer. By this reason, hydrogen-containing Flon compounds such ashydrofluorocarbons (HFC) and hydrochlorofluorocarbons (HCFC) areattracting attention as the novel kinds of the refrigerant. The termFlon compound described above and hereinafter stands for achlorofluorocarbon, a hydrofluorocarbon and a hydrochlorofluorocarbon ingeneral. The hydrogen-containing fluorocarbons, particularlyhydrofluorocarbons (HFC) represented by 1,1,1,2-tetrafluoroethane(referred to as Flon 134a hereinafter), are preferred as the refrigerantfor compression-type refrigerators because they have little possibilityof causing the rupture of the ozone layer and can replace Flon 12 withlittle change of the structure of refrigerators which have heretoforebeen used.

When a hydrogen-containing Flon compound described above, such as Flon134a and the like, is adopted as the refrigerant for compression-typerefrigerators to replace Flon 12, a lubricating oil having goodcompatibility with the hydrogen-containing Flon compound, such as Flon134a and the like, and good lubricating property satisfying therequirements described above is naturally required. However, because thelubricating oils used in combination with Flon 12 heretofore do not havegood compatibility with the hydrogen-containing Flon, such as Flon 134aand the like, a new lubricating oil suited for these compounds isrequired. When a new lubricating oil is adopted in accordance withreplacement of Flon 12, it is desired that major change of the structureof the apparatus is not necessary. It is not desirable that thestructure of the currently used apparatus must have major changesbecause of a lubricating oil.

As the lubricating oil having the compatibility with Flon 134a, forexample, lubricating oils of polyoxyalkylene glycols have been known.For example, Research Disclosure No. 17463 (October, 1978), thespecification of the U.S. Pat. No. 4,755,316, Japanese PatentApplication Laid Open No. 1989-256594, Japanese Patent Application LaidOpen No. 1989-259093, Japanese Patent Application Laid Open No.1989-259094, Japanese Patent Application Laid Open No. 1989-271491,Japanese Patent Application Laid Open No. 1990-43290, Japanese PatentApplication Laid Open No. 1990-84491, Japanese Patent Applications LaidOpen No. 1990-132176 to 132178, Japanese Patent Application Laid OpenNo. 1990-132179, Japanese Patent Application Laid Open No. 1990-173195,Japanese Patent Applications Laid Open No. 1990-180986 to 180987,Japanese Patent Applications Laid Open No. 1990-182780 to 182781,Japanese Patent Application Laid Open No. 1990-242888, Japanese PatentApplication Laid Open No. 1990-258895, Japanese Patent Application LaidOpen No. 1990-269195, Japanese Patent Application Laid Open No.1990-272097, Japanese Patent Application Laid Open No. 1990-305893,Japanese Patent Application Laid Open No. 1991-28296, Japanese PatentApplication Laid Open No. 1991-33193, Japanese Patent Applications LaidOpen No. 1991-103496 to 103497, Japanese Patent Application Laid OpenNo. 1991-50297, Japanese Patent Application Laid Open No. 1991-52995,Japanese Patent Applications Laid Open No. 1991-70794 to 70795, JapanesePatent Application Laid Open No. 1991-79696, Japanese Patent ApplicationLaid Open No. 1991-106992, Japanese Patent Application Laid Open No.1991-109492, Japanese Patent Application Laid Open No. 1991-121195,Japanese Patent Application Laid Open No. 1991-205492, Japanese PatentApplication Laid Open No. 1991-231992, Japanese Patent Application LaidOpen No. 1991-231994, Japanese Patent Application Laid Open No.1992-15295, Japanese Patent Application Laid Open No. 1992-39394 andJapanese Patent Applications Laid Open No. 1992-41591 to 41592 disclosedsuch lubricating oils. However, the lubricating oils of polyoxyalkyleneglycols generally have low volume specific resistances and no examplesatisfying the value of 10¹² Ω·cm or more at 80° C. has been disclosedyet.

As the compound having the compatibility with Flon 134a in addition tothe lubricating oils of polyoxyalkylene glycols, lubricating oils ofesters were disclosed in British Patent Laid Open No. 2216541, WO No.6979 (1990), Japanese Patent Applications Laid Open No. 1990-276894,Japanese Patent Applications Laid Open No. 1991-128992, Japanese PatentApplications Laid Open No. 1991-88892, Japanese Patent Applications LaidOpen No. 1991-179091, Japanese Patent Applications Laid Open No.1991-252497, Japanese Patent Applications Laid Open No. 1991-275799,Japanese Patent Applications Laid Open No. 1992-4294, Japanese PatentApplications Laid Open No. 1992-20597 and the specification of the U.S.Pat. No. 5,021,179. However, it is inevitable because of the structuralcharacteristic that carboxylic acids are formed by hydrolysis of thelubricating oils of esters.

Lubricating oils of carbonates were disclosed in Japanese PatentApplication Laid Open No. 1991-149295, European Patent No. 421298,Japanese Patent Application Laid Open No. 1991-217495, Japanese PatentApplication Laid Open No. 1991-247695, Japanese Patent Application LaidOpen No. 1992-18490 and Japanese Patent Application Laid Open No.1992-63893. However, the lubricating oils of carbonates have the sameproblem of hydrolysis as the lubricating oils of esters.

Thus, it is the real situation at present that a lubricating oil for thecompression-type refrigerators having excellent compatibility with Flon134a, excellent stability and lubricating property and a volume specificresistance at 80° C. of 10¹² Ω·cm or more has not been discovered yet.Development of such a lubricant is strongly desired.

Concerning generally known polyalkyl vinyl ethers, examples of synthesisof various kinds of alkyl polyvinyl ether are described in "JikkenKagaku Koza", Volume 18, "Reaction of organic compounds II(A)", editedby Chemical Society of Japan (published by Maruzen). Ends of thesepolymers are olefins in the case of the acid catalysts and acetals whenan alcohol is present in addition to the acid catalyst. When water ispresent, ends of acetal and ends of aldehyde are also formed. The end ofolefin causes coloring and increase of viscosity in the presence of anacid and the end of aldehyde also causes coloring. Acetals aredecomposed to olefins and alcohols in the presence of an acid. Theolefins react with each other to cause coloring and increase ofviscosity and, when water is present additionally, aldehydes are formed,also causing coloring. However, a polyvinyl ether compound which doesnot contain these structures causing degradation, such as the structuresof acetals, aldehydes and olefins, at the end of the molecule has notbeen reported yet.

SUMMARY OF THE INVENTION

The present invention has an object of providing a method of efficientlyproducing an ether compound having a wide range of applications assolvent, lubricating oil and the like by hydrogenation of an acetalcompound or a ketal compound by using a catalyst having a sufficientreaction activity and excellent selectivity and causing no corrosion ofthe apparatus. The present invention has another object of providing anovel polyvinyl ether compound favorably utilized particularly as thelubricating oil for compression-type refrigerators having sufficientcompatibility with hydrogen-containing Flon compounds, such as Flon134a, excellent stability and lubricating property and a volume specificresistance at 80° C. of 10¹² Ω·cm or more.

As the result of the intensive studies by the present inventors forachieving the first object described above, it was discovered that theobject can be achieved by using a solid catalyst having acidic propertyand hydrogenating ability as the catalyst. Furthermore, as the result ofthe intensive studies for achieving the second object of the presentinvention, it was discovered that the object can achieved by a polymerof an alkyl vinyl ether of a specific structure which does not containany of an unsaturated bond, an acetal structure and an aldehydestructure and has the weight average molecular weight in a specificrange. The present invention was completed on the basis of thesediscoveries.

Thus, the first of the present invention provides a method of productionof an ether compound expressed by the general formula (II) or (III):##STR1## wherein R¹ and R² are a hydrocarbon group or a hydrocarbongroup containing ether oxygens in the main chain, in the side chain orin the both of them, respectively, and may be the same or different fromeach other and R³, R⁴ and R⁵ are a hydrogen atom, a hydrocarbon group ora hydrocarbon group containing ether oxygens in the main chain, in theside chain or in the both of them, respectively, and may be the same ordifferent from each other, comprising bringing an acetal compound or aketal compound expressed by the general formula (I): ##STR2## whereinR¹, R², R³, R⁴ and R⁵ are the same as those in the general formulae (II)and (III), into the reaction with hydrogen in the presence of a solidcatalyst having acidic property and hydrogenating ability.

The second of the present invention provides a polyvinyl ether compoundcomprising constituting units expressed by the general formula (IX):##STR3## wherein R¹⁰, R¹¹ and R¹² are a hydrogen atom or an alkyl grouphaving 1 to 4 carbon atoms, respectively, and may be the same ordifferent from each other, R¹³ is an alkylene group having 2 to 4 carbonatoms, R¹⁴ is an alkyl group having 1 to 10 carbon atoms, m is a numberthe average of which is in the range of 0 to 10, R¹⁰ to R¹⁴ may be thesame or different between the constituting units and a plural of R¹³ O'smay be the same or different from each other when the constituting unitcontains a plural of R¹³ O's, does not contain any of an unsaturatedbond, an acetal structure and an aldehyde structure in the molecule andhas a weight average molecular weight of 300 to 3000.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 and FIG. 2 are a ¹ H-NMR chart of the acetal oligomer produced inExample 3 (1) and a ¹ H-NMR chart of the ether compound produced inExample 3 (2), respectively. FIG. 3, FIG. 6, FIG. 9, FIG. 12, FIG. 15,FIG. 16, FIG. 19, FIG. 22, FIG. 25 and FIG. 28 are the infraredabsorption spectra of the polyvinyl ether compounds obtained in Examples10, 11, 12, 13, 14, 15, 16, 17, 18 and 19, respectively. FIG. 4, FIG. 7,FIG. 10, FIG. 13, FIG. 17, FIG. 20, FIG. 23, FIG. 26 and FIG. 29 are the¹ H-NMR charts of the polyvinyl ether compounds obtained in Examples 10,11, 12, 13, 15, 16, 17, 18 and 19, respectively. FIG. 5, FIG. 8, FIG.11, FIG. 14, FIG. 18, FIG. 21, FIG. 27 and FIG. 30 are the ¹³ C-NMRcharts of the polyvinyl ether compounds obtained in Examples 10, 11, 12,13, 15, 16, 17, 18 and 19, respectively.

DESCRIPTION OF PREFERRED EMBODIMENTS

The ether compound of the first object of the present invention isdescribed first.

In the method of production of an ether compound of the presentinvention, an acetal compound or a ketal compound expressed by thegeneral formula (I): ##STR4## is used as the starting material. In thegeneral formula (I), R¹ and R² are, respectively, a hydrocarbon groupsuch as methyl group, ethyl group, n-propyl group, isopropyl group andthe like, or a hydrocarbon group containing ether oxygens in the mainchain, in the side chain or in the both of them, such as the groupsexpressed by the general formulae: ##STR5## wherein R is a hydrocarbongroup having 1 to 10 carbon atoms and r is an integer of 1 to 500. R¹and R² may be the same or different from each other. R³, R⁴ and R⁵ are ahydrogen atom, a hydrocarbon group or a hydrocarbon group containingether oxygens in the main chain, in the side chain or in the both ofthem, respectively. Examples of the hydrocarbon group or the hydrocarbongroup containing ether oxygens are the same groups as those shown asexamples in the description of R¹ and R² and groups expressed by thegeneral formula: ##STR6## wherein R and r are the same as thosedescribed above. R³, R⁴ and R⁵ may be the same or different from eachother.

In the present invention, an ether compound expressed by the generalformula (II) or (III): ##STR7## wherein R¹, R² R³, R⁴ and R⁵ are thesame as those described above, is obtained by the reaction of the acetalcompound or the ketal compound expressed by the general formula (I) withhydrogen in the presence of a solid catalyst having acidic property andhydrogenating ability.

As the acetal compound or the ketal compound expressed by the generalformula (I), a compound expressed by the general formula (IV): ##STR8##wherein R⁶ and R⁷ are a hydrocarbon group having 1 to 20 carbon atoms ora hydrocarbon group containing ether oxygens, respectively, and may bethe same or different from each other, R⁶ is the same or differentbetween the constituting units and n is an integer of 1 to 500, ispreferred and, in this case, a compound expressed by the general formula(V) or (VI): ##STR9## wherein R⁶, R⁷ and n are the same as thosedescribed above, is obtained as the ether compound.

In the compound expressed by the general formula (IV), a compoundexpressed by the general formula (XIV): ##STR10## wherein R⁶ and n arethe same as those describe above, is occasionally contained. When amixture like this is used, the ether compound obtained is the compoundexpressed by the general formula (V) described above or a mixture of thecompound expressed by the general formula (V) and the compound expressedby the general formula (VI).

As the acetal compound and the ketal compound expressed by the generalformula (I), a compound expressed by the general formula (VII):

    R.sup.8 CH(OR.sup.9).sub.2                                 (VII),

wherein R⁸ and R⁹ are a hydrocarbon group having 1 to 20 carbon atoms,respectively, and may the same or different from each other, is alsofavorably used. In this case, a compound expressed by the generalformula (VIII):

    R.sup.8 CH.sub.2 OR.sup.9                                  (VIII)

wherein R⁸ and R⁹ are the same as those described above, is obtained asthe ether compound.

In the method of the present invention, a solid catalyst having acidicproperty and hydrogenating ability is utilized. As the solid catalysthaving acidic property and hydrogenating ability, either a combinationof two kinds of catalyst which are a hydrogenation catalyst and a solidacid catalyst or a solid acid catalyst having hydrogenating ability isutilized.

The hydrogenation catalyst is not particularly limited and various kindsof generally used hydrogenation catalyst can be utilized. For example,(1) catalysts of an elementary metal like nickel, palladium, rhodium,platinum, ruthenium and the like and catalysts containing these metalsas the main components, (2) catalysts having the metal catalystcomponent of (1) supported on activated charcoal, alumina, diatomaceousearth or the like and (3) Raney catalysts like Raney nickel, Raneycobalt and the like are particularly effective.

The solid acid catalyst is not particularly limited and various kinds ofgenerally used solid acid catalyst can be used. For example, activatedclay, acidic clay, various kinds of zeolite, ion exchange resins,silica-alumina, heteropolyacids and the like are particularly effective.

The solid acid catalyst having hydrogenating ability is not particularlylimited and various kinds of generally used solid acid catalyst havinghydrogenating ability can be used. For example, catalysts in whichnickel, palladium, rhodium, platinum, ruthenium or the like is supportedon various kinds of zeolite are particularly effective.

The amount of the catalyst preferable for performing the method of thepresent invention is as following. When the combined catalyst is used,the amount of the hydrogenation catalyst is 0.1 to 50 weight % and theamount of the solid catalyst is 0.1 to 50 weight % based on the amountof the reacting materials, respectively. When the solid acid catalysthaving the hydrogenating ability is used, the amount is 0.1 to 50 weight% based on the amount of the reacting materials. When the amount is lessthan 0.1 weight %, the reaction does not proceed sufficiently. When theamount is more than 50 weight %, the amount of the catalyst based on theamount of the reacting materials is too much and the problem of decreaseof the productivity arises.

In the present invention, the acetal compound or the ketal compoundexpressed by the general formula (I) is brought into reaction withhydrogen in the presence of the catalyst described above. It ispreferable that hydrogen gas and the acetal compound or the ketalcompound are brought into contact with each other in the tool ratio of1:10 to 200:1. When the mol ratio is less than the specified range, thereaction does not proceed sufficiently. When the mol ratio is more thanthe specified range, the problem of decrease of the productivity arises.

The preferred conditions of the reaction for performing the reaction bythe method of the present invention are: the reaction temperature, 10°to 250° C.; the partial pressure of hydrogen, 1 to 200 kg/cm² ; the timeof reaction in the case of the batch reaction, 0.1 to 10 hours; and inthe case of the reaction in the liquid flow system, the weight spacevelocity (WHSV) of the reacting fluid, 0.01 to 100/hour; and the gasspace velocity (GHSV) of hydrogen gas, 100 to 10000/hour.

The reaction can be performed without a solvent but a solvent may beused when the solvent is stable at the reaction conditions. Examples ofthe solvents which can be used are hydrocarbon solvents, such as hexane,heptane, octane and the like.

By the reaction described above, --OR¹ group or --OR² group whichconstitutes a part of the acetal compound or the ketal compoundexpressed by the general formula (I) is eliminated from the acetalcompound or the ketal compound and replaced with a hydrogen to form theether compound expressed by the general formula (II) or the generalformula (III). In this reaction, it was made clear that, when any of R¹to R⁵ is a hydrocarbon group containing ether oxygens, hydrogen does notreact with the ether oxygen but reacts with the oxygen in the part ofthe acetal or the ketal alone.

After the reaction is finished, the reaction product can be separatedfrom the catalyst by the ordinary filtration or decantation. Thecatalyst separated here can be used again without particular treatment.

The reaction product may be formed into the product through processeslike distillation, extraction, washing, drying and the like according tonecessity.

The novel polyvinyl ether compound as the second object of the presentinvention is described in the following.

The polyvinyl ether compounds of the present invention comprises theconstituting units expressed by the general formula (IX): ##STR11## Inthe general formula (IX) described above, R¹⁰, R¹¹ and R¹² are ahydrogen atom or an alkyl group having 1 to 4 carbon atoms,respectively. Examples of the alkyl group are methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group and tert-butyl group. R¹⁰, R¹¹ and R¹² may be the sameor different from each other. Among hydrogen atom and the groupsdescribed above, hydrogen atom, methyl group and ethyl group arepreferable and it is preferred that at least one of R¹⁰, R¹¹ and R¹² ishydrogen atom.

R¹³ in the general formula (IX) is an alkylene group having 2 to 4carbon atoms and, more specifically, ethylene group, trimethylene group,methylethylene group, tetramethylene group, 1,1-dimethylethylene groupor 1,2-dimethylethylene group. Among them, alkylene groups having 2 or 3carbon atoms are particularly preferable. In the general formula (IX), mis the number of repeating of R¹³ O, the average of which is in therange of 0 to 10 and preferably in the range of 0 to 5.

R¹⁴ in the general formula (IX) is an alkyl group having 1 to 10 carbonatoms. Examples of the alkyl group are alkyl groups, such as methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,isobutyl group, sec-butyl group, tert-butyl group, various kinds ofpentyl group, various kinds of hexyl group, various kinds of heptylgroups, various kinds of octyl group and the like, cycloalkyl groups,such as cyclopentyl group, cyclohexyl group, various kinds ofmethylcyclohexyl group, various kinds of ethylcyclohexyl group, variouskinds of dimethylcyclohexyl group and the like, and the like groups.Among them, alkyl groups having 8 or less carbon atoms are preferable.Alkyl groups having 1 to 6 carbon atoms are particularly preferable whenm is 0 and alkyl groups having 1 to 4 carbon atoms are particularlypreferable when m is 1 or more.

R¹⁰ to R¹⁴ may be the same or different between the constituting unitsand a plural of R¹³ O's may be the same or different from each otherwhen the constituting unit contains a plural of R¹³ O's.

It is necessary that the polyvinyl ether compound of the presentinvention does not contain any of an unsaturated bond, an acetalstructure and an aldehyde structure in the molecule. The polyvinyl ethercompound generally has the structure in which one end is expressed bythe general formula (X): ##STR12## wherein R¹⁵, R¹⁶ and R¹⁷ are ahydrogen atom or an alkyl group having 1 to 4 carbon atoms,respectively, and may be the same or different from each other, R¹⁸ isan alkylene group having 2 to 4 carbon atoms, R¹⁹ is an alkyl grouphaving 1 to 10 carbon atoms, k is a number the average of which is inthe range of 0 to 10 and a plural of R¹⁸ O's may be the same ordifferent from each other, and the other end is expressed by the generalformula (XI): ##STR13## wherein R²⁰, R²¹ and R²² are a hydrogen atom oran alkyl group having 1 to 4 carbon atoms, respectively, and may be thesame or different from each other, R²³ is an alkylene group having 2 to4 carbon atoms, R²⁴ is an alkyl group having 1 to10 carbon atoms, p is anumber the average of which is in the range of 0 to 10 and a plural ofR²³ O's may be the same or different from each other.

In the general formula (X) described above, R¹⁵, R¹⁶ and R¹⁷ are ahydrogen atom or an alkyl group having 1 to4 carbon atoms, respectively.Examples of the alkyl group are the same as those shown as examples inthe description of R¹⁰ to R¹² in the general formula (IX). R¹⁵, R¹⁶ andR¹⁷ may be the same or different from each other. Among them, a hydrogenatom, methyl group and ethyl group are preferable and it is preferredthat at least one of R¹⁵, R¹⁶ and R¹⁷ is a hydrogen atom.

R¹⁸ in the general formula (X) is an alkylene group having 2 to 4 carbonatoms. Examples of the alkylene group are the same as those shown asexamples in the description of R¹³ in the general formula (IX). Amongthem, alkylene groups having 2 or 3 carbon atoms are particularlypreferable. In the general formula (X), k shows the repeating number ofR¹⁸ O, the average of which is in the range of 0 to 10 and preferably inthe range of 0 to 5. When a plural of R¹⁸ O's are comprised, a plural ofR¹⁸ O's may be the same or different from each other.

R¹⁹ in the general formula (X) is an alkyl group having 1 to 10 carbonatoms. Examples of the alkyl group are the same as those shown asexamples in the description of R¹⁴ in the general formula (IX). Amongthem, alkyl groups having 8 or less carbon atoms are preferable. Alkylgroups having 1 to6 carbon atoms are particularly preferable when k is 0and alkyl groups having 1 to4 carbon atoms are particularly preferablewhen k is 1 or more.

In the general formula (XI) described above, R²⁰, R²¹ and R²² are ahydrogen atom or an alkyl group having 1 to 4 carbon atoms,respectively. Examples of the alkyl group are the same as those shown asexamples in the description of R¹⁰ to R¹² in the general formula (IX).R²⁰, R²¹ and R²² may be the same or different from each other. Amongthem, a hydrogen atom, methyl group and ethyl group are preferable andit is preferred that at least one of R²⁰, R²¹ and R²² is a hydrogenatom.

R²³ in the general formula (XI) is an alkylene group having 2 to 4carbon atoms. Examples of the alkylene group are the same as those shownas examples in the description of R¹³ in the general formula (IX). Amongthem, alkylene groups having 2 or 3 carbon atoms are particularlypreferable. In the general formula (XI), p shows the repeating number ofR²³ O, the average of which is in the range of 0 to 10 and preferably inthe range of 0 to 5. When a plural of R²³ O's are comprised, a plural ofR²³ O's may be the same or different from each other.

R²⁴ in the general formula (XI) is an alkyl group having 1 to 10 carbonatoms. Examples of the alkyl group are the same as those shown asexamples in the description of R¹⁴ in the general formula (IX). Amongthem, alkyl groups having 8 or less carbon atoms are preferable. Alkylgroups having 1 to 6 carbon atoms are particularly preferable when p is0 and alkyl groups having 1 to 4 carbon atoms are particularlypreferable when p is 1 or more.

The polyvinyl ether compound of the present invention has the weightaverage molecular weight in the range of 300 to 3000, preferably thedegree of polymerization in the range of 5 to 10 and the weight averagemolecular weight in the range of 400 to 2000 and more preferably theweight average molecular weight in the range of 400 to 1000. The ratioof the weight average molecular weight to the number average molecularweight is in the range of 1.05 to 2.00 and preferably in the range of1.06 to 1.90.

The preferable compounds among the polyvinyl ether compounds of thepresent invention are compounds which have the constituting unitsexpressed by the general formula (XII): ##STR14## wherein R²⁵ is analkyl group having 1 to 4 carbon atoms and may be the same or differentbetween the constituting units, do not contain any of an unsaturatedbond, an acetal structure and an aldehyde structure and the weightaverage molecular weight in the range of 300 to 3000. The morepreferable compounds among them are compounds which have theconstituting units expressed by the general formula (XIII): ##STR15##wherein R²⁵ is the same as described above and q is the degree ofpolymerization, and the weight average molecular weight in the range of300 to 3000, more preferably in the range of 400 to 1000.

The polyvinyl ether compound of the present invention can be produced by(a) the process of polymerization of the corresponding vinyl ethermonomer and (b) the process of treatment of unsaturated bonds andacetals in the polymerized product.

(a) Process of polymerization

In the process of polymerization, the compound expressed by the generalformula (XV): ##STR16## wherein R¹⁰ to R¹⁴ and m are the same as thosedescribed above, is used as the vinyl ether monomer. As this vinyl ethermonomer, various kinds of compound corresponding to the polyvinyl ethercompounds described above are mentioned. Examples of such vinyl ethermonomer are: vinyl methyl ether, vinyl ethyl ether, vinyl n-propylether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether,vinyl sec-butyl ether, vinyl tert-butyl ether, vinyl n-pentyl ether,vinyl n-hexyl ether, vinyl 2-methoxyethyl ether, vinyl 2-ethoxyethylether, vinyl 2-methoxy-1-methylethyl ether, vinyl 2-methoxypropyl ether,vinyl 3,6-dioxaheptyl ether, vinyl 3,6,9-trioxadecyl ether, vinyl1,4-dimethyl-3,6-dioxaheptyl ether, vinyl1,4,7-trimethyl-3,6,9-trioxadecyl ether, 1-methoxypropene,1-ethoxypropene, 1-n-propoxypropene, 1-isopropoxypropene,1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene,1-tert-butoxypropene, 2-methoxypropene, 2-ethoxypropene,2-n-propoxypropene, 2-isopropoxypropene, 2-n-butoxypropene,2-isobutoxypropene, 2-sec-butoxypropene, 2-tert-butoxypropene,1-methoxy-1-butene, 1-ethoxy-1-butene, 1-n-propoxy-1-butene,1-isopropoxy-1-butene, 1-n-butoxy-1 -butene, 1-isobutoxy-1-butene,1-sec-butoxy-1-butene, 1-tert-butoxy-1-butene, 2-methoxy-1-butene,2-ethoxy-1-butene, 2-n-propoxy-1-butene, 2-isopropoxy-1-butene,2-n-butoxy-1-butene, 2-isobutoxy-1-butene, 2-sec-butoxy-1-butene,2-tert-butoxy-1-butene, 2-methoxy-2-butene, 2-ethoxy-2-butene,2-n-propoxy-2-butene, 2-isopropoxy-2-butene, 2-n-butoxy-2-butene,2-isobutoxy-2-butene, 2-sec-butoxy-2-butene, 2-tert-butoxy-2-butene andthe like. These vinyl ether monomers can be used singly or as acombination of two or more kinds. These vinyl ether monomers can beproduced by conventional methods. As the method of polymerization of thevinyl ether monomers, radical polymerization, cationic polymerization orirradiation polymerization described in "Kobunshi Gosei III", edited byShunsuke Murahashi, Minoru Imoto and Hisaya Tani (published by AsakuraShoten), can be adopted. A polymer having a desired viscosity can beobtained by the polymerization according to the method described in thefollowing.

For initiating the polymerization, a combination of a Br nsted acid, aLewis acid or an organometallic compound and water, an alcohol, aphenol, an acetal or an addition product of a vinyl ether and acarboxylic acid can be used as the initiator. Examples of the Br nstedacid are hydrofluoric acid, hydrochloric acid, hydrobromic acid,hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid,trifluoroacetic acid and the like. Examples of the Lewis acid are borontrifluoride, aluminum trichloride, aluminum tribromide, tintetrachloride, zinc dichloride, ferric chloride and the like. Amongthese Lewis acids, boron trifluoride and complexes thereof areparticularly preferable. Examples of the organometallic compound arediethyl aluminum chloride, ethyl aluminum chloride, diethylzinc and thelike.

As water, an alcohol, a phenol, an acetal or an addition product of avinyl ether and a carboxylic acid used in combination with thesecompounds, a suitable compound can be selected and used according todesire.

Examples of the alcohol described above are: saturated aliphaticalcohols having 1 to 10 carbon atoms, such as methanol, ethanol,propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol,various kinds of pentanol, various kinds of hexanol, various kinds ofheptanol, various kinds of octanol and the like; unsaturated aliphaticalcohols having 3 to 10 carbon atoms, such as allyl alcohol and thelike; alcohols containing oxygen bonded as the ether bond, such asethylene glycol monoalkyl ethers, ethylene glycol monoaryl ethers,propylene glycol monoalkyl ethers, propylene glycol monoaryl ethers,polyethylene glycol monoalkyl ethers, polyethylene glycol monoarylethers, polypropylene glycol monoalkyl ethers, polypropylene glycolmonoaryl ethers and the like; and the like compounds. Among thesecompounds, aliphatic alcohols having 3 or less carbon atoms arepreferable as the aliphatic alcohols and methanol and ethanol areparticularly preferable. As the alcohol containing oxygen bonded as theether bond, compounds of this structure having 14 or less carbon atomsare preferable.

Examples of the phenol are phenol, various kinds of cresol and the likecompounds.

Examples of the acetal are acetaldehyde dimethyl acetal, acetaldehydediethyl acetal, acetaldehyde methyl ethyl acetal, acetaldehydedi-n-propyl acetal, acetaldehyde methyl n-propyl acetal, acetaldehydeethyl n-propyl acetal, acetaldehyde diisopropyl acetal, acetaldehydemethyl isopropyl acetal, acetaldehyde ethyl isopropyl acetal,acetaldehyde n-propyl isopropyl acetal, acetaldehyde di-n-butyl acetal,acetaldehyde methyl n-butyl acetal, acetaldehyde ethyl n-butyl acetal,acetaldehyde n-propyl n-butyl acetal, acetaldehyde isopropyl n-butylacetal, acetaldehyde diisobutyl acetal, acetaldehyde methyl isobutylacetal, acetaldehyde ethyl isobutyl acetal, acetaldehyde n-propylisobutyl acetal, acetaldehyde isopropyl isobutyl acetal, acetaldehyden-butyl isobutyl acetal, acetaldehyde di-sec-butyl acetal, acetaldehydemethyl sec-butyl acetal, acetaldehyde ethyl sec-butyl acetal,acetaldehyde n-propyl sec-butyl acetal, acetaldehyde isopropyl sec-butylacetal, acetaldehyde n-butyl sec-butyl acetal, acetaldehyde isobutylsec-butyl acetal, acetaldehyde di-tert-butyl acetal, acetaldehyde methyltert-butyl acetal, acetaldehyde ethyl tert-butyl acetal, acetaldehyden-propyl tert-butyl acetal, acetaldehyde isopropyl tert-butyl acetal,acetaldehyde n-butyl tert-butyl acetal, acetaldehyde isobutyl tert-butylacetal, acetaldehyde sec-butyl tert-butyl acetal, acetaldehydedi(β-methoxyethyl) acetal, acetaldehyde di(β-methoxyisopropyl) acetal,propionaldehyde dimethyl acetal, propionaldehyde diethyl acetal,propionaldehyde methyl ethyl acetal, propionaldehyde di-n-propyl acetal,propionaldehyde methyl n-propyl acetal, propionaldehyde ethyl n-propylacetal, propionaldehyde diisopropyl acetal, propionaldehyde methylisopropyl acetal, propionaldehyde ethyl isopropyl acetal,propionaldehyde n-propyl isopropyl acetal, propionaldehyde di-n-butylacetal, propionaldehyde methyl n-butyl acetal, propionaldehyde ethyln-butyl acetal, propionaldehyde n-propyl n-butyl acetal, propionaldehydeisopropyl n-butyl acetal, propionaldehyde diisobutyl acetal,propionaldehyde methyl isobutyl acetal, propionaldehyde ethyl isobutylacetal, propionaldehyde n-propyl isobutyl acetal, propionaldehydeisopropyl isobutyl acetal, propionaldehyde n-butyl isobutyl acetal,propionaldehyde di-sec-butyl acetal, propionaldehyde methyl sec-butylacetal, propionaldehyde ethyl sec-butyl acetal, propionaldehyde n-propylsec-butyl acetal, propionaldehyde isopropyl sec-butyl acetal,propionaldehyde n-butyl sec-butyl acetal, propionaldehyde isobutylsec-butyl acetal, propionaldehyde di-tert-butyl acetal, propionaldehydemethyl tert-butyl acetal, propionaldehyde ethyl tert-butyl acetal,propionaldehyde n-propyl tert-butyl acetal, propionaldehyde isopropyltert-butyl acetal, propionaldehyde n-butyl tert-butyl acetal,propionaldehyde isobutyl tert-butyl acetal, propionaldehyde sec-butyltert-butyl acetal, propionaldehyde di(β-methoxyethyl) acetal,propionaldehyde di(b-methoxyisopropyl) acetal, n-butyraldehyde dimethylacetal, n-butyraldehyde diethyl acetal, n-butyraldehyde methyl ethylacetal, n-butyraldehyde di-n-propyl acetal, n-butyraldehyde methyln-propyl acetal, n-butyraldehyde ethyl n-propyl acetal, n-butyraldehydediisopropyl acetal, n-butyraldehyde methyl isopropyl acetal,n-butyraldehyde ethyl isopropyl acetal, n-butyraldehyde n-propylisopropyl acetal, n-butyraldehyde di-n-butyl acetal, n-butyraldehydemethyl n-butyl acetal, n-butyraldehyde ethyl n-butyl acetal,n-butyraldehyde n-propyl n-butyl acetal, n-butyraldehyde isopropyln-butyl acetal, n-butyraldehyde diisobutyl acetal, n-butyraldehydemethyl isobutyl acetal, n-butyraldehyde ethyl isobutyl acetal,n-butyraldehyde n-propyl isobutyl acetal, n-butyraldehyde isopropylisobutyl acetal, n-butyraldehyde n-butyl isobutyl acetal,n-butyraldehyde di-sec-butyl acetal, n-butyraldehyde methyl sec-butylacetal, n-butyraldehyde ethyl sec-butyl acetal, n-butyraldehyde n-propylsec-butyl acetal, n-butyraldehyde isopropyl sec-butyl acetal,n-butyraldehyde n-butyl sec-butyl acetal, n-butyraldehyde isobutylsec-butyl acetal, n-butyraldehyde di-tert-butyl acetal, n-butyraldehydemethyl tert-butyl acetal, n-butyraldehyde ethyl tert-butyl acetal,n-butyraldehyde n-propyl tert-butyl acetal, n-butyraldehyde isopropyltert-butyl acetal, n-butyraldehyde n-butyl tert-butyl acetal,n-butyraldehyde isobutyl tert-butyl acetal, n-butyraldehyde sec-butyltert-butyl acetal, n-butyraldehyde di(β-methoxyethyl) acetal,n-butyraldehyde di(β-methoxyisopropyl) acetal and the like.

Examples of the carboxylic acid utilized for forming the additionproduct with a vinyl ether are acetic acid, propionic acid, n-butyricacid, isobutyric acid, n-valeric acid, isovaleric acid, 2-methylbutyricacid, pivalic acid, n-caproic acid, 2,2-dimehylbutyric acid,2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid,enanthic acid, 2-methylcaproic acid, caprylic acid, 2-ethylcaproic acid,2-n-propylvaleric acid, n-nonanoic acid, 3,5,5-trimethylcaproic acid,undecanoic acid and the like. The vinyl ether may be the same as ordifferent from those utilized for the polymerization and the specificexamples are the same compounds as those mentioned as examples in thedescription of the vinyl ether monomers expressed by the general formula(XV). The addition product of the vinyl ether and the carboxylic acidcan be obtained by mixing these compounds and conducting the reaction ata temperature around 0° to 100° C. The product may be utilized for thereaction after isolation with distillation or the like and may also beutilized for the reaction without isolation.

To the initiated end of the polymer, hydrogen is attached when water, analcohol or a phenol is used and, when an acetal is used, the groupformed by elimination of one of the alkoxy groups from the used acetalis attached. When an addition product of a vinyl ether to a carboxylicacid is used, the group formed by elimination of the alkylcarbonyloxygroup derived from the carboxylic acid part from the addition product ofthe vinyl ether and the carboxylic acid is attached.

On the other hand, to the terminated end of the polymer, acetal, olefinor aldehyde is formed when water, an alcohol, a phenol or an acetal isused. When the addition product of a vinyl ether to a carboxylic acid isused, a carboxylic acid ester of hemiacetal is formed. When thecarboxylic acid ester of hemiacetal is hydrolyzed in the presence of anacid, an aldehyde is formed.

Polymerization of the vinyl ether monomer expressed by the generalformula (XV) is conducted at a temperature generally in the range of-80° to 150° C. and preferably 0° to 100° C. although the temperature isvaried depending on the kinds of the materials and the catalyst or theinitiator. The polymerization reaction is finished in a time of about 10seconds to 10 hours.

For adjusting the molecular weight in the polymerization reaction, apolymer having lower average molecular weight can be obtained byincreasing amount of an alcohol, water, a phenol, an acetal or theaddition product of a vinyl ether and a carboxylic acid relative to theamount of the vinyl ether monomer expressed by the general formula (IX).A polymer having lower average molecular weight can be obtained also byincreasing amount of the Br nsted acid or the Lewis acid describedabove.

The polymerization can be performed without a solvent but a solvent maybe used when the solvent is stable in the reaction condition. The kindof the solvent is not particularly limited. Preferable examples of thesolvent are hydrocarbon solvents, such as hexane, benzene, toluene andthe like, and ether solvents, such as ethyl ether, 1,2-dimethoxyethane,tetrahydrofuran and the like. The polymerization reaction can beterminated by adding an alkali.

(b) Process of treatment

In this process, unsaturated bonds, acetals and aldehydes in thepolymerized product are converted into saturated bonds and ethers.

(1) Unsaturated bond

Unsaturated bonds formed at the end of the polymer by the polymerizationcan be converted into saturated bonds in conventional conditions, suchas the reaction temperature of 20° to 200° C., the hydrogen pressure of1 to 100 kg/cm² and in the presence of a hydrogenation catalyst. As thehydrogenation catalyst, platinum catalysts, palladium catalysts, rhodiumcatalysts, ruthenium catalysts, nickel catalysts, cobalt catalysts andthe like are preferable.

The conversion can be performed also in the presence of the solidcatalyst having acidic property and hydrogenation ability used in themethod of production as the first object of the present inventiondescribed above.

(2) Acetal

The acetals can be efficiently converted to ethers by adopting themethod of production of an ether compound as the first object of thepresent invention described above which is the method of hydrogenationin the presence of the solid catalyst having acidic property andhydrogenating ability. As the solid catalyst having acidic property andhydrogenating ability and conditions of the reaction adopted here, thesolid catalyst and the conditions described in the method of productionof an ether compound can be adopted. According to the method of thepresent invention, the ether compound can be produced from the acetalcompound or the ketal compound with high conversion and highselectivity. In this process, because problem of corrosion does notarise, conventional apparatus of production can be used. Also, accordingto the method of the present invention, the acetal or the ketal ishydrogenized exclusively. Thus, even when the material acetal compoundor the material ketal compound contains a hydrocarbon group containingether oxygen, the part of ether oxygen is left unchanged and the acetalbond alone is converted to an ether bond.

The polyvinyl ether compound of the present invention is homopolymer ora copolymer of a vinyl ether monomer, contains none of unsaturatedbonds, acetal structures and aldehyde structures in the molecule, hassufficiently excellent compatibility particularly withhydrogen-containing Flons, such as Flon 134a and the like, has excellentstability and lubricating property, has a volume specific resistance at80° C. of 10¹² Ω·cm or more and is favorably used as a lubricating oilfor compression-type refrigerators.

The polyvinyl ether compound is useful also as an electric insulatingoil, an organic solvent, a surface active agent and the like.

The present invention is described with reference to examples in moredetail in the following. However, the present invention is not limitedby the examples.

The methods of measurements of the kinematic viscosity, the averagemolecular weights, the compatibility with Flon and the volume specificresistance and the method of hydrolysis testing of the polyvinyl ethercompound are shown in the following.

(1) Kinematic viscosity

Kinematic viscosity was measured according to the method of JapaneseIndustrial Standard K-2283 (1983) by using a glass capillary viscometer.

(2) Average molecular weights

Weight average molecular weight and number average molecular weight weremeasured by using the apparatus and in the conditions shown in thefollowing and dispersion (weight average molecular weight/number averagemolecular weight) was obtained from these results.

Apparatus: a product of Nippon Bunko Kogyo Co., Ltd., 880-PU (pump).

Shodex RI SE-61 (detector)

Column: TSK H8+G2000 H8+G1000 H8

Temperature: the room temperature

Solvent: THF (tetrahydrofuran)

Speed of elution: 1.4 ml/minute

Standard substance: polyethylene glycol

(3) Compatibility test

A sample of a specified amount adjusted to make 5 weight % or 10 weight% based on Flon 134a (1,1,1,2-tetrafluoroethane) was charged into apressure resistant glass ampoule and the ampoule was connected to thevacuum line and the line for Flon 134a gas. The ampoule was degassed invacuum at the room temperature, cooled with liquid nitrogen and aspecified amount of Flon 134a was taken into the ampoule. The ampoulewas then sealed and the temperature at which the phase separation startswas measured by slowly cooling the sample from the room temperature to-60° C. in a thermostatted vessel for the measurement of thecompatibility at the lower temperature side and by slowly heating thesample from the room temperature to +80° C. in a thermostatted vesselfor the measurement of the compatibility at the higher temperature side.A lower temperature of the phase separation is preferable in themeasurement at the lower temperature side and a higher temperature ofthe phase separation is preferable in the measurement at the highertemperature side.

(4) Volume specific resistance

A sample was dried under the reduced pressure (0.3 to 0.8 mmHg) at 100°C. for 1 hour and then charged into a liquid cell for the measurement ofvolume specific resistance which is placed into a thermostatted vesselat 80° C. After the sample was kept in the thermostatted vessel at 80°C. for 40 minutes, the volume specific resistance was measured at theadded electric pressure of 250 V by using an ultrainsulation meter R8340produced by Advantest Co.

(5) Hydrolysis test

Into a bottle of pressure resistant glass of 250 ml capacity, 75 g of asample, 25 g of water and a piece of copper (13×50 mm) were placed andthe atmosphere in the bottle was replaced with nitrogen. The sample waskept in a rotatory thermostatted vessel at the temperature of 102° C.for 192 hours. After finishing the test, appearance of the sample andcondition of the piece of copper were visually observed and the totalacid value was measured.

EXAMPLE OF CATALYST PREPARATION 1

Into a flask, 100 g (containing water) of Raney nickel (a product ofKawaken Fine Chemical Co., Ltd., M300T) was charged and 100 g ofabsolute ethanol was added to it and mixed well. The mixture was leftstanding to have Raney nickel precipitated and the supernatant liquidwas removed by decantation. The Raney nickel remaining in the flask wasrepeatedly treated with the treatment described above 5 times.

EXAMPLE OF CATALYST PREPARATION 2

Into a 100 ml flask of egg-plant type, 20 g of zeolite (a product ofToso Co., Ltd., HSZ330HUA) was charged. The flask was then dipped in anoil bath of 150° C. and evacuated by an oil rotary vacuum pump for 1hour. After cooling to the room temperature, the flask was brought tothe atmospheric pressure by introducing dry nitrogen.

EXAMPLE OF CATALYST PREPARATION 3

Into a 100 ml flask of egg-plant type, 20 g of activated clay (a productof Wako Jun-yaku Co., Ltd.) was charged. The flask was then dipped in anoil bath of 150° C. and evacuated by an oil rotary vacuum pump for 1hour. After cooling to the room temperature, the flask was brought tothe atmospheric pressure by introducing dry nitrogen.

EXAMPLE 1

Into a 1 liter autoclave made of SUS-316L, 100 g of acetaldehyde diethylacetal, 100 g of n-heptane, 3.0 g of Raney nickel prepared in Example ofCatalyst Preparation 1 (in the condition wet with ethanol) and 3.0 g ofzeolite prepared in Example of Catalyst Preparation 2 were charged.Hydrogen was introduced into the autoclave and the pressure of hydrogenwas adjusted to 10 kg/cm². After stirring for about 30 seconds, thepressure was released. Hydrogen was introduced into the autoclave againto make the pressure of hydrogen 10 kg/cm² and, after stirring for about30 seconds, the pressure of hydrogen was released. Then, the pressure ofhydrogen was increased to 30 kg/cm² and the temperature was increased to130° C. in 30 minutes under stirring. The reaction was conducted at 130°C. for 2 hours and 30 minutes. The reaction proceeded during and afterthe increase of the temperature and decrease of the hydrogen pressurewas observed. The increase of the pressure by the increase of thetemperature and the decrease of the pressure by the reaction weresuitably compensated by decreasing or increasing the pressure and thepressure of hydrogen was kept at 30 kg/cm² during the reaction. Afterfinishing the reaction, the reaction mixture was cooled to 20° C. andthe pressure was decreased to the atmospheric pressure. Qualitativeanalysis and quantitative analysis were made with the reaction solutionby the gas chromatography. The conversion of acetaldehyde diethyl acetalwas 94.9 % and the selectivity of diethyl ether was 68.3 %.

EXAMPLE 2

Into a 1 liter autoclave made of SUS-316L, 100 g of propionaldehydediethyl acetal, 100 g of n-octane, 6.0 g of Raney nickel prepared inExample of Catalyst Preparation 1 (in the condition wet with ethanol)and 6.0 g of zeolite prepared in Example of Catalyst Preparation 2 werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 10 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 10 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. Then, thepressure of hydrogen was increased to 30 kg/cm² and the temperature wasincreased to 130° C. in 30 minutes under stirring. The reaction wasconducted at 130° C. for 1 hour and 30 minutes. The reaction proceededduring and after the increase of the temperature and decrease of thehydrogen pressure was observed. The increase of the pressure by theincrease of the temperature and the decrease of the pressure by thereaction were suitably compensated by decreasing or increasing thepressure and the pressure of hydrogen was kept at 30 kg/cm² during thereaction. After finishing the reaction, the reaction mixture was cooledto 20° C. and the pressure was decreased to the atmospheric pressure.Qualitative analysis and quantitative analysis were conducted with thereaction product by the gas chromatography. The conversion ofpropionaldehyde diethyl acetal was 97.0 % and the selectivity of ethyln-propyl ether was 72.0 %.

EXAMPLE 3

(1) Preparation of Material

Into a 5 liter glass flask equipped with a dropping funnel, a cooler anda stirrer, 1000 g of toluene, 500 g of acetaldehyde diethyl acetal and5.0 g of boron trifluoride diethyl etherate were charged. Into adropping funnel, 2500 g of ethyl vinyl ether was charged and dropped in2 hours and 30 minutes. During this period, the reaction started and thetemperature of the reaction solution increased. The temperature was keptat about 25° C. by cooling with an ice water bath. After finishing thedropping, the solution was further stirred for 5 minutes. The reactionmixture was transferred to a washing vessel and washed with 1000 ml of a5 weight % aqueous solution of sodium hydroxide 3 times and then with1000 ml of water 3 times. The solvent and unreacted materials wereremoved under the reduced pressure by using a rotary evaporator toobtain 2833 g of the product. The ¹ H-NMR chart of this product is shownin FIG. 1. From this figure, the product was found to have thestructures of the following formulae (A) and (B). The product had thekinematic viscosity of 5.18 cSt at 100° C. and 38.12 cSt at 40° C.##STR17##

The ratio of numbers of molecule was (A):(B)=4.5:1 and the average valueof n was 5.6.

(2) Into a 1 liter autoclave made of SUS-316L, 200 g of the oligomerprepared in (1) described above, 6.0 g of Raney nickel prepared inExample of Catalyst Preparation 1 (in the condition wet with ethanol)and 6.0 g of zeolite prepared in Example of Catalyst Preparation 2 werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 10 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 10 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 25kg/cm² and the temperature was increased to 140° C. in 30 minutes understirring. The reaction was conducted at 140° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 25kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. To the reaction mixture, 100 mlof hexane was added. The catalyst was precipitated by standing for 30minutes and the reaction solution was removed by decantation. The hexanesolution was combined with the reaction solution and filtered withfilter paper. The catalyst was recycled in Example 5. Hexane, water andthe like were removed under the reduced pressure by using a rotaryevaporator. The yield was 162 g.

The ¹ H-NMR chart of this product is shown in FIG. 2. From this chart,the material acetal was found to have been converted to the ethercompound shown by the formula (C): ##STR18## wherein Et is an ethylgroup. The conversion was 100%. The kinematic viscosity was 4.90 at 100°C. and 29.50 at 40° C. The oligomer of ethyl vinyl ether having theformula (B) described above was also converted to the ether compoundhaving the formula (C) described above.

EXAMPLE 4

Into a 1 liter autoclave made of SUS-316L, 200 g of the oligomerprepared in Example 3 (1) described above, 20 g of Raney nickel preparedin Example of Catalyst Preparation 1 (in the condition wet with ethanol)and 20 g of zeolite prepared in Example of Catalyst Preparation 2 werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 7 kg/cm². After stirring for about 30 seconds,the pressure was released. After repeating this operation once more, thepressure of hydrogen was brought to 7 kg/cm² and the temperature wasincreased to 130° C. in 30 minutes under stirring. The reaction wasconducted at 130° C. for 2 hours and 30 minutes. The reaction proceededduring and after the increase of the temperature and decrease of thehydrogen pressure was observed. The increase of the pressure by theincrease of the temperature and the decrease of the pressure by thereaction were suitably compensated by decreasing or increasing thepressure and the pressure of hydrogen was kept at 7 kg/cm² during thereaction. After finishing the reaction, the reaction mixture was cooledto the room temperature and the pressure was decreased to theatmospheric pressure. The reaction mixture was filtered and water andthe like were removed from the solution part under the reduced pressureby using a rotary evaporator. The yield was 160 g. By this procedure,the same ether compound as that in Example 3 (2) was obtained from thematerial acetal and the conversion was 100%. The kinematic viscosity was4.77 at 100° C. and 30.27 at 40° C.

EXAMPLE 5

In the autoclave used in Example 3 (2) in which the catalyst wasremaining, 200 g of the oligomer prepared in Example 3 (1) was chargedand the reaction was performed by the same method as in Example 3 (2).The yield was 164 g. By this procedure, the same ether compound wasobtained as that in Example 3 (2) from the material acetal and theconversion was 100%. The kinematic viscosity was 4.93 at 100° C. and29.13 at 40° C.

EXAMPLE 6

(1) Preparation of Material

The reaction was performed by the same method as in Example 3 (1) exceptthat the amount of acetaldehyde diethyl acetal was 450 g, the amount ofboron trifluoride etherate was 4.5 g and the amount of ethyl vinyl etherwas 2800 g. The yield was 3175 g. The product had the same structure asthat in Example 3 (1). The kinematic viscosity was 6.79 at 100° C. and59.68 at 40° C. The ratio of the numbers of molecule was (A):(B)=8:1 andthe average value of n was 6.8.

(2) Into a 1 liter autoclave made of SUS-316L, 200 g of the oligomerprepared in (1) described above, 10 g of Raney nickel prepared inExample of Catalyst Preparation 1 (in the condition wet with ethanol)and 15 g of activated clay prepared in Example of Catalyst Preparation 3were charged. Hydrogen was introduced into the autoclave and thepressure of hydrogen was adjusted to 10 kg/cm². After stirring for about30 seconds, the pressure was released. Hydrogen was introduced into theautoclave again and the pressure of hydrogen was adjusted to 10 kg/cm².After stirring for about 30 seconds, the pressure was released. Afterrepeating this operation once more, the pressure of hydrogen wasincreased to 30 kg/cm² and the temperature was increased to 150° C. in40 minutes under stirring. The reaction was conducted at 150° C. for 1hour. The reaction proceeded during and after the increase of thetemperature and decrease of the hydrogen pressure was observed. Theincrease of the pressure by the increase of the temperature and thedecrease of the pressure by the reaction were suitably compensated bydecreasing or increasing the pressure and the pressure of hydrogen waskept at 30 kg/cm² during the reaction. After finishing the reaction, thereaction mixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The reaction mixture was filteredand water and the like were removed from the solution part under thereduced pressure by using a rotary evaporator. The yield was 158 g. Bythis procedure, the same ether compound as in Example 3 (2) was obtainedfrom the material acetal and the conversion was 100%. The kinematicviscosity was 7.06 at 100° C. and 57.32 at 40° C.

EXAMPLE 7

Into a 1 liter autoclave made of SUS-316L, 200 g of the oligomerprepared in Example 3 (1) described above, 10 g of zeolite prepared inExample of Catalyst Preparation 2 and 5.0 g of Pd/C (supporting 5% ofPd, a product of Wako Jun-yaku Co., Ltd.) were charged. Hydrogen wasintroduced into the autoclave and the pressure of hydrogen was adjustedto 7 kg/cm². After stirring for about 30 seconds, the pressure wasreleased. Hydrogen was introduced into the autoclave again and thepressure of hydrogen was adjusted to 7 kg/cm². After stirring for about30 seconds, the pressure was released. After repeating this operationonce more, the pressure of hydrogen was brought to 7 kg/cm² and thetemperature was increased to 120° C. in 30 minutes under stirring. Thereaction was conducted at 120° C. for 7 hours. The reaction proceededduring and after the increase of the temperature and decrease of thehydrogen pressure was observed. The increase of the pressure by theincrease of the temperature and the decrease of the pressure by thereaction were suitably compensated by decreasing or increasing thepressure and the pressure of hydrogen was kept at 7 kg/cm² during thereaction. After finishing the reaction, the reaction mixture was cooledto the room temperature and the pressure was decreased to theatmospheric pressure. The reaction mixture was filtered and water andthe like were removed from the solution part under the reduced pressureby using a rotary evaporator. The yield was 167.2 g. By this procedure,the same ether compound as in Example 3 (2) was obtained from thematerial acetal and the conversion was 100%. The kinematic viscosity was5.28 at 100° C. and 32.93 at 40° C.

EXAMPLE 8

Into a 1 liter autoclave made of SUS-316L, 200 g of the oligomerprepared in Example 3 (1) described above, 20 g of zeolite prepared inExample of Catalyst Preparation 2 and 20 g of Ru/C (supporting 5% of Ru,a product of Wako Jun-yaku Co., Ltd.) were charged. Hydrogen wasintroduced into the autoclave and the pressure of hydrogen was adjustedto 30 kg/cm². After stirring for about 30 seconds, the pressure wasreleased. Hydrogen was introduced into the autoclave again and thepressure of hydrogen was adjusted to 30 kg/cm². After stirring for about30 seconds, the pressure was released. After repeating this operationonce more, the pressure of hydrogen was brought to 30 kg/cm² and thetemperature was increased to 130° C. in 30 minutes under stirring. Thereaction was conducted at 130° C. for 1 hour. The reaction proceededduring and after the increase of the temperature and decrease of thehydrogen pressure was observed. The increase of the pressure by theincrease of the temperature and the decrease of the pressure by thereaction were suitably compensated by decreasing or increasing thepressure and the pressure of hydrogen was kept at 30 kg/cm² during thereaction. After finishing the reaction, the reaction mixture was cooledto the room temperature and the pressure was decreased to theatmospheric pressure. The reaction mixture was filtered and water andthe like were removed from the solution part under the reduced pressureby using a rotary evaporator. The yield was 156 g. By this procedure,the same ether compound as in Example 3 (2) was obtained from thematerial acetal and the conversion was 100%. The kinematic viscosity was5.18 at 100° C. and 31.53 at 40 ° C.

EXAMPLE 9

Into a 1 liter autoclave made of SUS-316L, 15 g of Ni-diatomaceous earthand 350 g of hexane were charged. After replacing the atmosphere in theautoclave with hydrogen, the pressure of hydrogen was adjusted to 30kg/cm². The temperature was increased to 150° C. in 30 minutes understirring and the activation treatment of the catalyst was conducted for30 minutes. After cooling the autoclave, 300 g of the oligomer preparedin Example 3 (1) and 15 g of zeolite prepared in Example of CatalystPreparation 2 were charged into the autoclave. Hydrogen was introducedinto the autoclave and the pressure of hydrogen was adjusted to 30kg/cm². After stirring for about 30 seconds, the pressure was released.Hydrogen was introduced into the autoclave again and the pressure ofhydrogen was adjusted to 30 kg/cm². After stirring for about 30 seconds,the pressure was released. After repeating this operation once more, thepressure of hydrogen was brought to 30 kg/cm² and the temperature wasincreased to 130° C. in 30 minutes under stirring. The reaction wasconducted at 130° C. for 1 hour. The reaction proceeded during and afterthe increase of the temperature and decrease of the hydrogen pressurewas observed. The increase of the pressure by the increase of thetemperature and the decrease of the pressure by the reaction weresuitably compensated by decreasing or increasing the pressure and thepressure of hydrogen was kept at 30 kg/cm² during the reaction. Afterfinishing the reaction, the reaction mixture was cooled to the roomtemperature and the pressure was decreased to the atmospheric pressure.The reaction mixture was filtered and hexane, water and the like wereremoved from the solution part under the reduced pressure by using arotary evaporator. The yield was 240 g.

The conversion of the material acetal was 100% like in Example 3. Thekinematic viscosity was 5.38 at 100° C. and 33.12 at 40° C.

EXAMPLE 10

(1) Preparation of polymer of ethyl vinyl ether

Into a 5 liter glass flask equipped with a dropping funnel, a cooler anda stirrer, 1000 g of toluene, 304 g of ethanol and 7.8 g of borontrifluoride diethyl etherate were charged. Into a dropping funnel, 3284g of ethyl vinyl ether was charged and dropped in 4 hours and 30minutes. The temperature of the reaction solution increased by the heatof reaction and the temperature was kept at about 25° C. by cooling withan ice water bath. After finishing the dropping, the solution wasfurther stirred for 5 minutes. The reaction mixture was transferred to awashing vessel and washed with 1100 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 1100 ml of water 3 times. Thesolvent and unreacted materials were removed under the reduced pressureby using a rotary evaporator to obtain 3397 g of the crude product. Thecrude product had the kinematic viscosity of 17.8 cSt at 40° C.

¹ H-NMR and ¹³ C-NMR of the crude product were measured. The ¹ H-NMRshowed peaks at 4.7 ppm, 5.35 ppm and 5.6 ppm and the ¹³ C-NMR showedpeaks at 101 ppm, 129 ppm and 134 ppm.

Into a 2 liter autoclave made of SUS-316L, 600 g of the crude product,600 g of hexane, 18 g of Raney nickel prepared in Example of CatalystPreparation 1 and 18 g of zeolite prepared in Example of CatalystPreparation 2 were charged. Hydrogen was introduced into the autoclaveand the pressure of hydrogen was adjusted to 20 kg/cm². After stirringfor about 30 seconds, the pressure was released. Hydrogen was introducedinto the autoclave again to make the pressure of hydrogen 20 kg/cm² and,after stirring for about 30 seconds, the pressure of hydrogen wasreleased. After repeating this operation once more, the pressure ofhydrogen was increased to 50 kg/cm² and the temperature was increased to140° C. in 30 minutes under stirring. The reaction was conducted at 140°C. for 2 hours. The reaction proceeded during and after the increase ofthe temperature and decrease of the hydrogen pressure was observed. Theincrease of the pressure by the increase of the temperature and thedecrease of the pressure by the reaction were suitably compensated bydecreasing or increasing the pressure and the pressure of hydrogen waskept at 50 kg/cm² during the reaction. After finishing the reaction, thereaction mixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was removed by decantation.The catalyst was washed with 100 ml of hexane twice. The washing liquidwas combined with the reaction liquid and filtered with filter paper.The combined liquid was then transferred to a washing vessel and washedwith 500 ml of a 5 weight % aqueous solution of sodium hydroxide 3 timesand then with 500 ml of distilled water 5 times. Hexane, water and thelike were removed under the reduced pressure by using a rotaryevaporator. The yield was 492 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the ethyl vinyl ether polymer obtainedin (1) described above were measured. The results of the measurementsare shown in Table 1.

The infrared absorption spectrum is shown in FIG. 3, the ¹ H-NMR chartis shown in FIG. 4 and the ¹³ C-NMR chart is shown in FIG. 5.

In the ¹ H-NMR chart of this polymer, the peaks at 4.7 ppm, 5.35 ppm and5.6 ppm observed in the chart of the crude product described above werenot found. In the ¹³ C-NMR chart of this polymer, the peaks at 101 ppm,129 ppm and 134 ppm were not found either. Furthermore, although the ¹H-NMR peak derived from the hydrogen of aldehyde is generally found inthe area of 9.7 ppm and the ¹³ C-NMR peak derived from the carbon ofaldehyde is generally found in the area of 200 ppm, none of these peakswere found in the spectra of the polymer obtained above.

From these findings, it can be found that the polymer obtained above didnot contain any of an unsaturated bond, an acetal structure and analdehyde structure.

EXAMPLE 11

(1) Preparation of Polymer of Ethyl Vinyl Ether

Into a 5 liter glass flask equipped with a dropping funnel, a cooler anda stirrer, 1000 g of toluene, 500 g of acetaldehyde diethyl acetal and5.0 g of boron trifluoride diethyl etherate were charged. Into adropping funnel, 2700 g of ethyl vinyl ether was charged and dropped in3 hours. The temperature of the reaction solution increased by the heatof reaction and the temperature was kept at about 25° C. by cooling withan ice water bath. After finishing the dropping, the solution wasfurther stirred for 5 minutes. The reaction mixture was transferred to awashing vessel and washed with 1000 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 1000 ml of water 3 times. Thesolvent and unreacted materials were removed under the reduced pressureby using a rotary evaporator to obtain 3040 g of the crude product. Thecrude product had the kinematic viscosity of 42.1 cSt at 40° C. Into a 2liter autoclave made of SUS-316L, 600 g of the crude product, 600 g ofhexane, 18 g of Raney nickel prepared in Example of Catalyst Preparation1 and 18 g of zeolite prepared in Example of Catalyst Preparation 2 werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 20 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 20 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 50kg/cm² and the temperature was increased to 140° C. in 30 minutes understirring. The reaction was conducted at 140° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 50kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 100 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper. The combined liquid was then transferred to a washingvessel and washed with 500 ml of a 5 weight % aqueous solution of sodiumhydroxide 3 times and then with 500 ml of distilled water 5 times.Hexane, water and the like were removed under the reduced pressure byusing a rotary evaporator. The yield was 495 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the ethyl vinyl ether polymer obtainedin (1) described above were measured. The results of the measurementsare shown in Table 1.

The infrared absorption spectrum is shown in FIG. 6, the ¹ H-NMR chartis shown in FIG. 7 and the ¹³ C-NMR chart is shown in FIG. 8.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 12

(1) Preparation of Polymer of Ethyl Vinyl Ether

Into a 5 liter glass flask equipped with a dropping funnel, a cooler anda stirrer, 1000 g of toluene, 450 g of acetaldehyde diethyl acetal and4.5 g of boron trifluoride diethyl etherate were charged. Into adropping funnel, 3200 g of ethyl vinyl ether was charged and dropped in4 hours and 10 minutes. The temperature of the reaction solutionincreased by the heat of reaction and the temperature was kept at about25° C. by cooling with an ice water bath. After finishing the dropping,the solution was further stirred for 5 minutes. The reaction mixture wastransferred to a washing vessel and washed with 1000 ml of a 5 weight %aqueous solution of sodium hydroxide 3 times and then with 1000 ml ofwater 3 times. The solvent and unreacted materials were removed underthe reduced pressure by using a rotary evaporator to obtain 3466 g ofthe crude product. The crude product had the kinematic viscosity of 76.1cSt at 40° C.

Into a 2 liter autoclave made of SUS-316L, 600 g of the crude product,600 g of hexane, 18 g of Raney nickel prepared in Example of CatalystPreparation 1 and 18 g of zeolite prepared in Example of CatalystPreparation 2 were charged. Hydrogen was introduced into the autoclaveand the pressure of hydrogen was adjusted to 20 kg/cm². After stirringfor about 30 seconds, the pressure was released. Hydrogen was introducedinto the autoclave again to make the pressure of hydrogen 20 kg/cm² and,after stirring for about 30 seconds, the pressure of hydrogen wasreleased. After repeating this operation once more, the pressure ofhydrogen was increased to 50 kg/cm² and the temperature was increased to140° C. in 30 minutes under stirring. The reaction was conducted at 140°C. for 2 hours. The reaction proceeded during and after the increase ofthe temperature and decrease of the hydrogen pressure was observed. Theincrease of the pressure by the increase of the temperature and thedecrease of the pressure by the reaction were suitably compensated bydecreasing or increasing the pressure and the pressure of hydrogen waskept at 50 kg/cm² during the reaction. After finishing the reaction, thereaction mixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 100 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper. The combined liquid was then transferred to a washingvessel and washed with 500 ml of a 5 weight % aqueous solution of sodiumhydroxide 3 times and then with 500 ml of distilled water 5 times.Hexane, water and the like were removed under the reduced pressure byusing a rotary evaporator. The yield was 498 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the ethyl vinyl ether polymer obtainedin (1) described above were measured. The results of the measurementsare shown in Table 1.

The infrared absorption spectrum is shown in FIG. 9, the ¹ H-NMR chartis shown in FIG. 10 and the ¹³ C-NMR chart is shown in FIG. 11.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 13

(1) Preparation of Polymer of Isopropyl Vinyl Ether

Into a 500 ml glass flask equipped with a dropping funnel, a cooler anda stirrer, 95 g of toluene, 14.7 g of isopropyl alcohol and 1.8 g ofboron trifluoride diethyl etherate were charged. Into a dropping funnel,190 g of isopropyl vinyl ether was charged and dropped in 30 minutes.The temperature of the reaction solution increased by the heat ofreaction and the temperature was kept at about 25° C. by cooling with anice water bath. After finishing the dropping, the solution was furtherstirred for 5 minutes. The reaction mixture was transferred to a washingvessel and washed with 70 ml of a 5 weight % aqueous solution of sodiumhydroxide 3 times and then with 70 ml of water 3 times. The solvent andunreacted materials were removed under the reduced pressure by using arotary evaporator to obtain 179 g of the crude product. The crudeproduct had the kinematic viscosity of 27.0 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 171 g of the crude product,130 g of hexane, 20 g of Raney nickel prepared in Example of CatalystPreparation 1 and 20 g of zeolite prepared in Example of CatalystPreparation 2 were charged. Hydrogen was introduced into the autoclaveand the pressure of hydrogen was adjusted to 20 kg/cm². After stirringfor about 30 seconds, the pressure was released. Hydrogen was introducedinto the autoclave again to make the pressure of hydrogen 20 kg/cm² and,after stirring for about 30 seconds, the pressure of hydrogen wasreleased. After repeating this operation once more, the pressure ofhydrogen was increased to 50 kg/cm² and the temperature was increased to130° C. in 30 minutes under stirring. The reaction was conducted at 130°C. for 1 hour. The reaction proceeded during and after the increase ofthe temperature and decrease of the hydrogen pressure was observed. Theincrease of the pressure by the increase of the temperature and thedecrease of the pressure by the reaction were suitably compensated bydecreasing or increasing the pressure and the pressure of hydrogen waskept at 50 kg/cm² during the reaction. After finishing the reaction, thereaction mixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 100 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper. The combined liquid was then transferred to a 2 literwashing vessel and washed with 50 ml of a 5 weight % aqueous solution ofsodium hydroxide 3 times and then with 50 ml of distilled water 5 times.Hexane, water and the like were removed under the reduced pressure byusing a rotary evaporator. The yield was 131 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the isopropyl vinyl ether polymerobtained in (1) described above were measured. The results of themeasurements are shown in Table 1.

The infrared absorption spectrum is shown in FIG. 12, the ¹ H-NMR chartis shown in FIG. 13 and the ¹³ C-NMR chart is shown in FIG. 14.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 14

(1) Preparation of Polymer of Isopropyl Vinyl Ether

Into a 1 liter glass flask equipped with a dropping funnel, a cooler anda stirrer, 250 g of toluene, 36.82 g of isopropyl alcohol and 4.35 g ofboron trifluoride diethyl etherate were charged. Into a dropping funnel,500 g of isopropyl vinyl ether was charged and dropped in 30 minutes.During this period, the reaction started and the temperature of thereaction solution increased. The temperature was kept at about 30° C. bycooling with an ice water bath. After finishing the dropping, thesolution was further stirred for 5 minutes. The reaction mixture wastransferred to a washing vessel and washed with 130 ml of a 3 weight %aqueous solution of sodium hydroxide 3 times and then with 200 ml ofwater 3 times. The solvent and unreacted materials were removed underthe reduced pressure by using a rotary evaporator to obtain 475.3 g ofthe crude product. The crude product had the kinematic viscosity of 32.4cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 380 g of the crude product,100 g of hexane, 45 g of Raney nickel prepared in Example of CatalystPreparation 1 and 45 g of zeolite prepared in Example of CatalystPreparation 2 were charged. Hydrogen was introduced into the autoclaveand the pressure of hydrogen was adjusted to 20 kg/cm². After stirringfor about 30 seconds, the pressure was released. Hydrogen was introducedinto the autoclave again to make the pressure of hydrogen 20 kg/cm² and,after stirring for about 30 seconds, the pressure of hydrogen wasreleased. After repeating this operation once more, the pressure ofhydrogen was increased to 50 kg/cm² and the temperature was increased to130° C. in 30 minutes under stirring. The reaction was conducted at 130°C. for 1 hour and 30 minutes. The reaction proceeded during and afterthe increase of the temperature and decrease of the hydrogen pressurewas observed. The increase or the pressure by the increase of thetemperature and the decrease of the pressure by the reaction weresuitably compensated by decreasing or increasing the pressure and thepressure of hydrogen was kept at 50 kg/cm² during the reaction. Afterfinishing the reaction, the reaction mixture was cooled to the roomtemperature and the pressure was decreased to the atmospheric pressure.The catalyst was precipitated by standing for 1 hour and the reactionliquid was separated by decantation. The catalyst was washed with 100 mlof hexane twice. The washing liquid was combined with the reactionliquid and filtered with filter paper. The combined liquid was thentransferred to a 2 liter washing vessel and washed with 200 ml of a 5weight % aqueous solution of sodium hydroxide 3 times and then with 200ml of distilled water 5 times. Hexane, water and the like were removedunder the reduced pressure by using a rotary evaporator. The yield was287 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the isopropyl vinyl ether polymerobtained in (1) described above were measured. The results of themeasurements are shown in Table 1.

The infrared absorption spectrum is shown in FIG. 15.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 15

(1) Preparation of Polymer of Methyl Vinyl Ether

Into a 200 ml stainless steel autoclave equipped with a stirrer, 40 g oftoluene, 6.4 g of methanol and 0.45 g of boron trifluoride diethyletherate were charged. The autoclave was tightly closed and theatmosphere in the autoclave was replaced with nitrogen. Into theautoclave, 107 g of methyl vinyl ether was added from a bomb by thepressure of the compound in 5 hours. The temperature of the reactionsolution increased by the heat of reaction and the temperature was keptat about 25° C. by cooling with an ice water bath. After finishing theaddition, the solution was further stirred for 10 minutes. The reactionmixture was transferred to a washing vessel and washed with 100 ml of a5 weight % aqueous solution of sodium hydroxide 3 times and then with150 ml of water 3 times. The solvent and unreacted materials wereremoved under the reduced pressure by using a rotary evaporator toobtain 95 g of the crude product. The crude product had the kinematicviscosity of 56.9 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 90 g of the crude product,300 g of hexane, 4.5 g of Raney nickel and 4.5 g of zeolite werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 20 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 20 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 50kg/cm² and the temperature was increased to 130° C. in 30 minutes understirring. The reaction was conducted at 130° C. for 1 hour. The reactionproceeded during and after the increase of the temperature and decreaseof the hydrogen pressure was observed. The increase of the pressure bythe increase of the temperature and the decrease of the pressure by thereaction were suitably compensated by decreasing or increasing thepressure and the pressure of hydrogen was kept at 50 kg/cm² during thereaction. After finishing the reaction, the reaction mixture was cooledto the room temperature and the pressure was decreased to theatmospheric pressure. The catalyst was precipitated by standing for 1hour and the reaction liquid was separated by decantation. The catalystwas washed with 30 ml of hexane twice. The washing liquid was combinedwith the reaction liquid and filtered with filter paper. After hexanewas removed under the reduced pressure by using a rotary evaporator, 100ml of toluene was added to the residual product and the product was thentransferred to a washing vessel and washed with 100 ml of a 5 weight %aqueous solution of sodium hydroxide 3 times and then with 150 ml ofdistilled water 5 times. Toluene, water and the like were removed underthe reduced pressure by using a rotary evaporator. The yield was 80.5 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the methyl vinyl ether polymer obtainedin (1) described above were measured. The results of the measurementsare shown in Table 1.

The infrared absorption spectrum is shown in FIG. 16, the ¹ H-NMR chartis shown in FIG. 17 and the ¹³ C-NMR chart is shown in FIG. 18.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 16

(1) Preparation of Copolymer of Ethyl Vinyl Ether and Isopropyl VinylEther

Into a 500 ml glass flask equipped with a dropping funnel, a cooler anda stirrer, 50 g of toluene, 17.7 g of acetaldehyde diethyl acetal and1.5 g of boron trifluoride diethyl etherate were charged. Into adropping funnel, 43 g of ethyl vinyl ether and 65 g of isopropyl vinylether were charged and dropped in 50 minutes. The temperature of thereaction solution increased by the heat of reaction and the temperaturewas kept at about 30° C. by cooling with an ice water bath. Afterfinishing the dropping, the solution was further stirred for 5 minutes.The reaction mixture was transferred to a washing vessel and washed with100 ml of a 5 weight % aqueous solution of sodium hydroxide 3 times andthen with 150 ml of water 3 times. The solvent and unreacted materialswere removed under the reduced pressure by using a rotary evaporator toobtain 120 g of the crude product. The crude product had the kinematicviscosity of 48.8 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 110 g of the crude product,300 g of hexane, 5.5 g of Raney nickel and 5.5 g of zeolite werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 20 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 20 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 50kg/cm² and the temperature was increased to 140° C. in 30 minutes understirring. The reaction was conducted at 140° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 50kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The reaction liquid was removedby decantation. The catalyst was washed with 30 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper. The filtered combined liquid is then transferred to awashing vessel and washed with 100 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 150 ml of distilled water 5times. Hexane, water and the like were removed under the reducedpressure by using a rotary evaporator. The yield was 97 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the ethyl vinyl ether/isopropyl vinylether copolymer obtained in (1) described above were measured. Theresults of the measurements are shown in Table 1.

The infrared absorption spectrum is shown in FIG. 19, the ¹ H-NMR chartis shown in FIG. 20 and the ¹³ C-NMR chart are shown in FIG. 21.

By the same reason as that described in Example 10, the copolymerobtained above did not contain any of an unsaturated bond, an acetalstructure and an aldehyde structure.

EXAMPLE 17

(1) Preparation of Polymer of Isobutyl Vinyl Ether

Into a 500 ml glass flask equipped with a dropping funnel, a cooler anda stirrer, 50 g of toluene, 11 g of isobutyl alcohol and 0.5 g of borontrifluoride diethyl etherate were charged. Into a dropping funnel, 100 gof isobutyl vinyl ether was charged and dropped in 55 minutes. Thetemperature of the reaction solution increased by the heat of reactionand the temperature was kept at about 30° C. by cooling with an icewater bath. After finishing the dropping, the solution was furtherstirred for 5 minutes. The reaction mixture was transferred to a washingvessel and washed with 100 ml of a 5 weight % aqueous solution of sodiumhydroxide 3 times and then with 150 ml of water 3 times. The solvent andunreacted materials were removed under the reduced pressure by using arotary evaporator to obtain 107 g of the crude product. The crudeproduct had the kinematic viscosity of 52.4 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 90 g of the crude product,300 g of hexane, 4.8 g of Raney nickel and 4.8 g of zeolite werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 20 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 20 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 50kg/cm² and the temperature was increased to 140° C. in 30 minutes understirring. The reaction was conducted at 140° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 50kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 30 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper.

The combined liquid was then transferred to a 1 liter washing vessel andwashed with 100 ml of a 5 weight % aqueous solution of sodium hydroxide3 times and then with 150 ml of distilled water 5 times. Hexane, waterand the like were removed under the reduced pressure by using a rotaryevaporator. The yield was 80.5 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the isobutyl vinyl ether polymerobtained in (1) described above were measured. The results of themeasurements are shown in Table 1.

The infrared absorption spectrum is shown in FIG. 22, the ¹ H-NMR chartis shown in FIG. 23 and the ¹³ C-NMR chart is shown in FIG. 24.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 18

(1) Preparation of Polymer of 1-ethoxy-1-propene

Into a 500 ml glass flask equipped with a dropping funnel, a cooler anda stirrer, 80 g of toluene, 40 g of propionaldehyde diethyl acetal and0.4 g of boron trifluoride diethyl etherate were charged. Into adropping funnel, 116 g of 1-ethoxy-1-propene was charged and dropped in60 minutes. The temperature of the reaction solution increased by theheat of reaction and the temperature was kept at about 30° C. by coolingwith an ice water bath. After finishing the dropping, the solution wasfurther stirred for 40 minutes. The reaction mixture was transferred toa washing vessel and washed with 150 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 200 ml of water 3 times. Thesolvent and unreacted materials were removed under the reduced pressureby using a rotary evaporator to obtain 140 g of the crude product. Thecrude product had the kinematic viscosity of 34.4 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 120 g of the crude product,300 g of hexane, 6 g of Raney nickel and 6 g of zeolite were charged.Hydrogen was introduced into the autoclave and the pressure of hydrogenwas adjusted to 20 kg/cm². After stirring for about 30 seconds, thepressure was released. Hydrogen was introduced into the autoclave againto make the pressure of hydrogen 20 kg/cm² and, after stirring for about30 seconds, the pressure of hydrogen was released. After repeating thisoperation once more, the pressure of hydrogen was increased to 50 kg/cm²and the temperature was increased to 130° C. in 30 minutes understirring. The reaction was conducted at 130° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 50kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 50 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper.

The combined liquid was then transferred to a 1 liter washing vessel andwashed with 150 ml of a 5 weight % aqueous solution of sodium hydroxide3 times and then with 200 ml of distilled water 5 times. Hexane, waterand the like were removed under the reduced pressure by using a rotaryevaporator. The yield was 95 g.

(2) Evaluation

Kinematic viscosity, average molecular weights and dispersion ofmolecular weight, compatibility with Flon, volume specific resistanceand resistance to hydrolysis of the 1-ethoxy-1-propene polymer obtainedin (1) described above were measured. The results of the measurementsare shown in Table 1.

The infrared absorption spectrum is shown in FIG. 25, the ¹ H-NMR chartis shown in FIG. 26 and the ¹³ C-NMR chart is shown in FIG. 27.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

EXAMPLE 19

(1) Preparation of polymer of methoxyethyl vinyl ether

Into a 500 ml glass flask equipped with a dropping funnel, a cooler anda stirrer, 100 g of toluene, 21.3 g of acetaldehyde dimethoxyethylacetal and 0.45 g of boron trifluoride diethyl etherate were charged.Into a dropping funnel, 112 g of methoxyethyl vinyl ether was chargedand dropped in 50 minutes. The temperature of the reaction solutionincreased by the heat of reaction and the temperature was kept at about25° C. by cooling with an ice water bath. After finishing the dropping,the solution was further stirred for 5 minutes. The reaction mixture wastransferred to a washing vessel and 200 ml of chloroform was added toit. The product was washed with 100 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 150 ml of water 3 times. Thesolvent and unreacted materials were removed under the reduced pressureby using a rotary evaporator to obtain 129 g of the crude product. Thecrude product had the kinematic viscosity of 33.3 cSt at 40° C.

Into a 1 liter autoclave made of SUS-316L, 110 g of the crude product,300 g of hexane, 5.5 g of Raney nickel and 5.5 g of zeolite werecharged. Hydrogen was introduced into the autoclave and the pressure ofhydrogen was adjusted to 20 kg/cm². After stirring for about 30 seconds,the pressure was released. Hydrogen was introduced into the autoclaveagain to make the pressure of hydrogen 20 kg/cm² and, after stirring forabout 30 seconds, the pressure of hydrogen was released. After repeatingthis operation once more, the pressure of hydrogen was increased to 50kg/cm² and the temperature was increased to 130° C. in 30 minutes understirring. The reaction was conducted at 130° C. for 2 hours. Thereaction proceeded during and after the increase of the temperature anddecrease of the hydrogen pressure was observed. The increase of thepressure by the increase of the temperature and the decrease of thepressure by the reaction were suitably compensated by decreasing orincreasing the pressure and the pressure of hydrogen was kept at 50kg/cm² during the reaction. After finishing the reaction, the reactionmixture was cooled to the room temperature and the pressure wasdecreased to the atmospheric pressure. The catalyst was precipitated bystanding for 1 hour and the reaction liquid was separated bydecantation. The catalyst was washed with 30 ml of hexane twice. Thewashing liquid was combined with the reaction liquid and filtered withfilter paper. Hexane was removed from the combined liquid under thereduced pressure by using a rotary evaporator and 200 ml of chloroformwas added to the remaining product. The product was then transferred toa washing vessel and washed with 100 ml of a 5 weight % aqueous solutionof sodium hydroxide 3 times and then with 150 ml of distilled water 5times. The solvent, water and the like were removed under the reducedpressure by using a rotary evaporator. The yield was 94 g.

(2) Evaluation

Kinematic viscosity, compatibility with Flon and resistance tohydrolysis of the methoxyethyl vinyl ether polymer obtained in (1)described above were measured. The results of the measurements are shownin Table 1.

The infrared absorption spectrum is shown in FIG. 28, the ¹ H-NMR chartis shown in FIG. 29 and the ¹³ C-NMR chart is shown in FIG. 30.

By the same reason as that described in Example 10, the polymer obtainedabove did not contain any of an unsaturated bond, an acetal structureand an aldehyde structure.

                                      TABLE I                                     __________________________________________________________________________    kinematic                     volume specific                                 viscosity     molecular weight                                                                              resistance                                      (cSt)         weight                                                                             number     at 80° C.                                      40° C.                                                                     100° C.                                                                    average                                                                            average                                                                            dispersion                                                                          (Ω · cm)                         __________________________________________________________________________    Example 10                                                                          16.5                                                                              3.41                                                                              492  439  1.12  2.3 × 10.sup.13                           Example 11                                                                          31.6                                                                              5.15                                                                              615  529  1.16  1.5 × 10.sup.14                           Example 12                                                                          55.2                                                                              7.32                                                                              722  608  1.19  5.8 × 10.sup.13                           Example 13                                                                          28.3                                                                              4.37                                                                              570  462  1.23  5.3 × 10.sup.13                           Example 14                                                                          22.8                                                                              3.77                                                                              547  470  1.16  6.1 × 10.sup.12                           Example 15                                                                          74.4                                                                              8.60                                                                              798  488  1.64  4.4 × 10.sup.12                           Example 16                                                                          40.0                                                                              5.85                                                                              706  525  1.35  1.9 × 10.sup.13                           Example 17                                                                          59.0                                                                              7.05                                                                              996  524  1.90  1.4 × 10.sup.13                           Example 18                                                                          26.8                                                                              4.20                                                                              436  396  1.10  6.5 × 10.sup.13                           Example 19                                                                          30.4                                                                              6.29                                                                              --   --   --    --                                              __________________________________________________________________________           compatibility with Flon 134a                                                  temperature of separation                                                                     temperature of separation                                     at low temperature (°C.)                                                               at high temperature (°C.)                              5%    10%       5%    10%                                              __________________________________________________________________________    Example 10                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 11                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 12                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 13                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 14                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 15                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 16                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 17                                                                           insoluble                                                                           insoluble insoluble                                                                           insoluble                                        Example 18                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            Example 19                                                                           -60.0>                                                                              -60.0>    80.0< 80.0<                                            __________________________________________________________________________    after the hydrolysis test                                                             sample oil                                                                             total acid value                                                                      appearance                                                 appearance (mg KOH/g)                                                                            of piece of copper                                   __________________________________________________________________________    Example 10                                                                          good       0.5>    good                                                 Example 11                                                                          good       0.5>    good                                                 Example 12                                                                          good       0.5>    good                                                 Example 13                                                                          good       0.5>    good                                                 Example 14                                                                          good       0.5>    good                                                 Example 15                                                                          good       0.5>    good                                                 Example 16                                                                          good       0.5>    good                                                 Example 17                                                                          good       0.5>    good                                                 Example 18                                                                          good       0.5>    good                                                 Example 19                                                                          good       0.5>    good                                                 __________________________________________________________________________

What is claimed is:
 1. A method of production of an ether compoundexpressed by the general formula (II): ##STR19## or by the generalformula (III): ##STR20## wherein R¹ and R² are a hydrocarbon group or ahydrocarbon group containing ether oxygens in the main chain, in theside chain or in the both of them, respectively, and may be the same ordifferent from each other and R³, R⁴ and R⁵ are a hydrogen atom, ahydrocarbon group or a hydrocarbon group containing ether oxygens in themain chain, in the side chain or in the both of them, respectively, andmay be the same or different from each other, which comprises bringingan acetal compound or a ketal compound expressed by the formula (I):##STR21## wherein R¹, R², R³, R⁴ and R⁵ are the same as those in thegeneral formulae (II) and (III), into the reaction at a temperature of10°-250° C. with hydrogen at a pressure of 1-200 kg/cm² in the presenceof solid catalyst consisting of a combination of a hydrogenationcatalyst and a solid acid catalyst.
 2. A method of production of anether compound as claimed in claim 1, wherein the acetal compound or theketal compound expressed by the formula (I) is a compound expressed bythe formula (IV): ##STR22## wherein R⁶ and R⁷ are a hydrocarbon grouphaving 1 to 20 carbon atoms or a hydrocarbon group containing etheroxygens, respectively, and may be the same or different from each other,R⁶ may be the same or different between the constituting units and n isan integer of 1 to 500, and the ether compound obtained is a compoundexpressed by the formula (V): ##STR23## or by the formula (VI):##STR24## wherein R⁶, R⁷ and n are the same as those in the formula(IV).
 3. A method of production of an ether compound as claimed in claim1, wherein the acetal compound or the ketal compound expressed by theformula (I) is a compound expressed by the formula (VII):

    R.sup.8 CH(OR.sup.9).sub.2                                 (VII),

wherein R⁸ and R⁹ are a hydrocarbon group having 1 to 20 carbon atoms,respectively, and may the same or different from each other, and theether compound obtained is a compound expressed by the formula (VIII):

    R.sup.8 CH.sub.2 OR.sup.9                                  (VIII),

wherein R⁸ and R⁹ are the same as those in the formula (VII).